Smoking cigarettes and e-cigarettes is widely popular among Chinese students. Considering that school personnel are considered role models in the student community, we investigated the prevalence and determinants of such behavior among high school personnel in China so as to provide references for future related intervention measures. We used a stratified cluster sampling design on a total number of 3311 school employees recruited from 33 representative schools. Complex sampling analysis and logistic regressions were used for univariate and multivariate analyses. Among 3194 participants that met the study criteria, 7.4% were cigarette users, and 3.6% e-cigarette consumers. For conventional cigarette smokers, certain characteristics, such as being older and male, attaining less education, and having been exposed to secondhand smoke, were associated with heavier smoking. Nevertheless, e-cigarette users were predominantly male and of younger age. Those who understood the hazards of conventional cigarette smoking had less inclination to smoke but were at a higher risk of e-cigarette use. Our analysis suggests that it is necessary to target different populations for monitoring and controlling conventional cigarette smoking and e-cigarette use respectively among school personnel. In addition, China is in need of more relevant and strict anti-smoking regulations.